Schiff base derivatives of ruthenium and osmium olefin metathesis catalysts

Abstract

The present invention generally relates to ruthenium and osmium carbene catalysts for use in olefin metathesis reactions. More particularly, the present invention relates to Schiff base derivatives of ruthenium and osmium carbene catalysts and methods for making the same. The inventive catalysts are generally prepared by the treatment of unmodified catalysts with the salts of the desired Schiff base ligands, in which an anionic and a neutral electron donating ligands of the unmodified catalysts are simultaneously replaced. The Schiff base derivatives of the ruthenium and osmium carbene catalysts show unexpectedly improved thermal stability while maintaining high metathesis activity, even in polar protic solvents. Although the inventive catalysts may be used in all metathesis reactions, use of these catalysts for ring-closing metathesis ("RCM") reactions is particularly preferred.

What is claimed is: 
     
       1. A compound of the general formula of the formula ##STR16## wherein: M is ruthenium or osmium; X 1  an anionic ligand;   L 1  is a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl and C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   Z is selected from the group consisting of oxygen, sulfur, --NR 10 , and --PR 10 , and   R 6 , R 7 , R 8 , R 9 , and R 10  are each selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, each non-hydrogen group optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   wherein X 1 , L 1 , Z, R, R 1 , R 6 , R 7 , R 8 , and R 9  each optionally includes one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.   
     
     
       2. The compound of claim 1 wherein M is ruthenium;   R is hydrogen;   R 1  is selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, and aryl;   L 1  is a phosphine of the formula PR 3  R 4  R 5  wherein R 3 , R 4 , and R 5  are each selected from the group consisting of aryl, C 1  -C 10  primary alkyl, secondary alkyl, and cycloalkyl; and,   X 1  is selected from the group consisting of halide, CF 3  CO 2 , CH 3  CO 2 , CFH 2  CO 2 , (CH 3 ) 3  CO, (CF 3 ) 2  (CH 3 )CO, (CF 3 )(CH 3 ) 2  CO, PhO, MeO, EtO, tosylate, mesylate, and, trifluoromethanesulfonate.   
     
     
       3. The compound as in claim 2 wherein: X 1  is chloride;   L 1  is selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3 , and -P(phenyl) 3  ;   R 1  is phenyl or vinyl, optionally substituted with one or more moeties selected from the group consisting of C 5  -C 5  alkyl, C 5  -C 5  alkoxy, and phenyl;   R 6  and R 7  together form an aryl or heteroaryl group;   R 8  is hydrogen; and,   R 9  is aryl or heteroaryl.   
     
     
       4. The compound as in claim 3 wherein R 6  and R 7  together forms a phenyl group; and,   R 9  is phenyl.   
     
     
       5. A compound of the formula ##STR17## wherein: X 1  is an anionic ligand; L 1  is a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   R 9  is selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, the non-hydrogen groups optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl; and,   R 11  is an aryl or heteroaryl, optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   wherein X 1 , L 1 , R, R 1 , R 9 , and R 11  each optionally includes one or more functional groups selected from the group consisting hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.   
     
     
       6. The compound as in claim 5 wherein X 1  is selected from the group consisting of halide, CF 3  CO 2 , CH 3  CO 2 , CFH 2  CO 2 , (CH 3 ) 3  CO, (CF 3 ) 2  (CH 3 )CO, (CF 3 )(CH 3 ) 2  CO, PhO, MeO, EtO, tosylate, mesylate, and, trifluoromethanesulfonate;   L 1  is a phosphine of the formula PR 3  R 4  R 5  where R 3 , R 4 , and R 5  are each selected from the group consisting of aryl, C 1  -C 10  primary alkyl, secondary alkyl, and cycloalkyl;   R is hydrogen; and,   R 1  is selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, and aryl.   
     
     
       7. The compound as in claim 6 wherein X 1  is chloride;   L 1  is selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3  ; and -P(phenyl) 3  ;   R 1  is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1  -C 5  alkyl, C 1  -C5 alkoxy, and phenyl; and,   R 9  and R 11  are each aryl or heteroaryl.   
     
     
       8. The compound as in claim 7 wherein R 9  and R 11  are each phenyl.   
     
     
       9. The compound as in claim 7 wherein R 9  and R 11  are both phenyl substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl, the R 9  and R 11  groups each optionally including one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. 
     
     
       10. The compound as in claim 9 having the formula ##STR18## 
     
     
       11. A method for preparing a catalyst having the formula comprising contacting a salt of a Schiff base having the formula ##STR19## with compound having the formula ##STR20## wherein: M is ruthenium or osmium; X and X 1  are each an anionic ligand;   L and L 1  are each a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl and C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   Z is selected from the group consisting of oxygen, sulfur, --NR 10 , and --PR 10 , and   R 6 , R 7 , R 8 , R 9 , and R 10  are each selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, each non-hydrogen group optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   wherein X 1 , L 1 , Z, R, R 1 , R 6 , R 7 , R 8 , and R 9  each optionally includes one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.   
     
     
       12. The method as in claim 11 wherein the salt of the Schiff base is a thallium salt. 
     
     
       13. The method as in claim 12 wherein M is ruthenium;   R is hydrogen;   R 1  is selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, and aryl;   L and L 1  are each a phosphine of the formula PR 3  R 4  R 5  where R 3 , R 4 , and R 5  are each selected from the group consisting of aryl, C 1  -C 10  primary alkyl, secondary alkyl, and cycloalkyl; and,   X and X 1  are each selected from the group consisting of halide, CF 3  CO 2 , CH 3  CO 2 , CFH 2  CO 2 , (CH 3 ) 3  CO, (CF 3 ) 2  (CH 3 )CO, (CF 3 )(CH 3 ) 2  CO, PhO, MeO, EtO, tosylate, mesylate, and, trifluoromethanesulfonate.   
     
     
       14. The compound as in claim 13 wherein: X and X 1  are each chloride;   L and L 1  are each selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3  ; and -P(phenyl) 3  ;   R 1  is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1  -C 5  alkyl, C 1  -C 5  alkoxy, and phenyl;   R 6  and R 7  together form an aryl or heteroaryl group;   R 8  is hydrogen; and,   R 9  is aryl or heteroaryl.   
     
     
       15. The compound as in claim 14 wherein R 6  and R 7  together forms a phenyl group; and,   R 9  is phenyl.   
     
     
       16. A method of preparing a catalyst having the formula ##STR21## comprising contacting a salt a Schiff base having the formula R 11  (HC═NR 9 )(O 31  ) with a compound having the formula ##STR22## wherein: X 1  are each an anionic ligand; L and L 1  are each a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl and C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   R 9  is selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, the non-hydrogen groups optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl; and,   R 11  is an aryl or heteroaryl, optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl, wherein X 1 , L 1 , R, R 1 , R 9 , and R 11  each optionally includes one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.     
     
     
       17. The method as in claim 16 wherein the salt of the Schiff base is a thallium salt. 
     
     
       18. The method as in claim 16 wherein X and X 1  are each selected from the group consisting of halide, CF 3  CO 2 , CH 3  CO 2 , CFH 2  CO 2 , (CH 3 ) 3  CO, (CF 3 ) 2  (CH 3 )CO, (CF 3 )(CH 3 ) 2  CO, PhO, MeO, EtO, tosylate, mesylate, and, trifluoromethanesulfonate;   L and L 1  are each a phosphine of the formula PR 3  R 4  R 5  where R 3 , R 4 , and R 5  are each aryl, C 1  -C 10  primary alkyl, secondary alkyl, or cycloalkyl;   R is hydrogen; and,   R 1  is selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, and aryl.   
     
     
       19. The method as in claim 18 wherein X and X 1  are each chloride;   L and L 1  are each -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3 , and -P(phenyl) 3  ;   R 1  is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1  -C 5  alkyl, C 1  -C 5  alkoxy, and phenyl; and   R 9  and R 11  are each aryl or heteroaryl.   
     
     
       20. The method as in claim 19 wherein R 9  and R 11  are each phenyl.   
     
     
       21. The method as in claim 19 wherein R 9  and R 11  are both phenyl substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl; the R 9  and R 11  groups each optionally including one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. 
     
     
       22. The method as in claim 21 wherein the catalyst has the formula ##STR23## 
     
     
       23. A method for performing a metathesis reaction comprising contacting an olefin with a catalyst having the formula wherein: M is ruthenium or osmium;   X 1  is an anionic ligand;   L 1  is a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl and C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   Z is selected from the group consisting of oxygen, sulfur, --NR 10 , and --PR 10 , and   R 6 , R 7 , R 8 , R 9 , and R 10  are each selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, each non-hydrogen group optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl; wherein X 1 , L 1 , Z, R, R 1 , R 6 , R 7 , R 8 , and R 9  each optionally includes one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.     
     
     
       24. The method as in claim 23 wherein the olefin is a cyclic olefin. 
     
     
       25. A method for molding articles comprising (i) adding to a mold at room temperature an olefin and a catalyst having the formula ##STR24##  wherein: M is ruthenium or osmium; X 1  is an anionic ligand;   L 1  is a neutral electron donor;   R and R 1  are each hydrogen or a substituent selected from the group consisting of C 1  -C 20  alkyl, C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, aryl, C 1  -C 20  carboxylate, C 1  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl and C 1  -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   Z is selected from the group consisting of oxygen, sulfur, --NR 10 , and --PR 10 , and   R 6 , R 7 , R 8 , R 9 , and R 10  are each selected from the group consisting of hydrogen, C 1  -C 20  alkyl, aryl, and heteroaryl, each non-hydrogen group optionally substituted with one or more moieties selected from the group consisting of C 1  -C 10  alkyl, C 1  -C 10  alkoxy, and aryl;   wherein X 1 , L 1 , Z, R, R 1 , R 6 , R 7 , R 8 , and R 9  each optionally includes one or more functional groups selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen and     (ii) bringing the mold to a temperature of at least 40° C.